Access JEE Advanced Revision Notes Chemistry Principles of

Qualitative Analysis
Introduction
Qualitative Inorganic analysis deals with the identification of radicals present in
salt.
Cation derived from the base is termed as basic radical.

Anion derived from acid is termed an acidic radical.

Example:

Physical Properties of Salts:

Observation Inference

The substance is coloured

Light pink Hydrated salt of Mn

Reddish pink Hydrated salt of Co(II)

Red

, some dichromats and

Orange-red
ferricyanides

Redish brown Ferric chloride, Fe2O3

,
Light yellow or brown
a few iodides and ferrocyanides.
salts, hydrated ferrous salts,
Green
some compounds

Dark green Salt of Cr(III)

Blue

Sulphide of Cu(II) and Fe(II),

Black

Light yellow or brown Ferric salts

Substance Smells
 Ammonium carbonates and other
Ammoniacal smell
Ammonium salts.

Bitter almond type Cyanides

Vinegar or acetic acid

Acetates
type

Chlorine gas smell Hypochlorites.

Solution is Colored

Green or blue

Pink Mn2+ and Co2+

Yellow CrO42-, Fe3+,

Dichromate (orange),
Orange or purple
Permanganates(Purples).

Substance is heavy Salt of Pb and Hg

The substance is light Carbonates of Mg, Al, Zn, Ca, Sr, Bi

Heating Effects on Various Salts

S.No Observation Inference

Substance decrepitates
1
(Cracking noise)

Salts of alkali metals and salts having water of

2 Substance melts
crystallization.

Substance swells
3 (due to loss of water of Alums, borates and Phosphates.
crystallization)

4 The substance sublimes and the color of sublimate is:

White

and (turns red when rubbed with

Yellow a glass rod)
Iodides
Blue-black and violet vapor

5 A residue (general oxides) is left and its color is

Yellow (hot) and White (cold) ZnO

Reddish-brown (hot), Yellow PbO

Black (hot); Red (cold) HgO,

Black (hot); Red-brown (cold)

6 Gas is evolved

Colorless and odorless

-turns lime water milky

-rekindle a glowing splinter Alkali Nitrates

Ammonium nitrite

Colorless gas with odor:

turns red litmus blue

Ammonium salts
and mercurous nitrate paper
black

- Smell of burning sulfur,

Sulphites and thiosulphates
turns acidified
paper green

HCl- Pungent smell, white Hydrated chlorides

fumes with ammonia

Coloured gas:

- Brown turns starch Nitrites and nitrates of heavy metals

iodide paper blue.

Dry Tests:
These texts give a clear indication of the presence of certain radicals.

Flame Test:
The flame test should not be performed in the presence of As, Sb, Bi, Sn and Pb
as these radical form alloy with Pt, and wire may be spoiled.

Colour of Flame Inference

Pale greenish Pb

Green with a blue center Cu

Apple green Ba

Crimson red Sr, Li

Brick red Ca

Pink violet (Lilac) K

Golden yellow Na

Violet Rb, Cs

Livid blue As, Bi

Borax Bead Test:

On heating Borax, the colorless glassy bead formed, which consists of

sodium metaborate and boric anhydride.

Oxidising Flame: On heating with a colored salt, the glassy bead forms a
colored metaborate.
 Reducing Atmosphere: Borax bead test can be carried out in the reducing
atmosphere by using a charcoal cavity. The carbon background will act as
reducing the atmosphere.

Oxidizing Flame Reducing Flame Metal

Blue Red Copper

Yellow Green Iron

Green Green Chromium

Violet Colourless Manganese

Blue Blue Cobalt

Red-brown Grey Nickel

Identification of Acidic Radicals (or) Anions

Most of the salts are reacted with (or) dil HCl and
are release characteristic gas with acidic radicals.

But some anions are not decomposed either by or

.

Hence acidic radicals have been classified into three groups, depending
upon salt response to a reagent.

Group-I: Contains the radicals which are detected by (or) dil HCl.
They are

a. Carbonates

b. Sulphite

c. Sulphide
 d. Nitrite

e. Acetate
Group-II: Contains the radicals which are detected by

a. Chloride

b. Bromide

c. Iodide

d. Nitrate

e. Oxalate

Group-III: Contains the radicals which don’t give any characteristic gas with
dilute and .

They are:

a. Sulphate

b. Phosphate

1. Reaction of ions:
i) With Dilute HCl: gives effervescence, due to the evolution of carbon dioxide.

The gas carbon dioxide turns lime water milky white ppt

The gas gives turbidity with lime water and baryta water.

On prolonged passage of carbon dioxide in lime water, the turbidity sluggishly

disappears due to the conformation of answerable hydrogen carbonate.

ii) Barium Chloride or Calcium Chloride Solution:

White ppt of barium or calcium carbonate is obtained, which is soluble in
mineral acid.
The ppt is soluble in mineral acids and carbonic acid(soda water).

iii) Silver Nitrate Solution:

White ppt of silver carbonate is obtained.

The ppt so attained is soluble in nitric acid and in ammonia.

The ppt becomes brown on addition of excess reagent and the same may also
be if the blend is boiled, due to the conformation of tableware oxide

2. Sulphites
i) Dilute HCl or Dilute
decomposes with the evolution of sulfur dioxide

The gas has a suffocating odor of burning sulfur.

ii) Acidified potassium dichromate solution:

Turns sludge paper moistened with acidified potassium dichromate result, green
due to the conformation of ions.

iii) Lime water: On passing the gas through lime water, a milky ppt is formed.
The precipitate dissolves on prolonged passage of the gas, due to the
conformation of hydrogen sulfite ions.

iv) Barium chloride or Strontium chloride solution: Gives white ppt. of barium or
strontium sulfite.

3. Sulphide
i) Dil. HCl or Dil. :
A colorless gas smelling of rotten eggs is evolved.
ii) The gas turns lead acetate paper black

iii) Silver nitrate solution: Black ppt. of silver sulfide insoluble in cold but soluble in
hot dil nitric acid.

iv) Sodium Nitroprusside Solution: Turns sodium nitroprusside solution purple

4. Nitrites
i) Dil HCl and Dil. : Adding to solid nitrite in cold yields pale blue liquid
(due to the presence of free nitrous acid or its anhydride & the
evolution of brown fumes of nitrogen dioxide, the latter being largely produced
by a combination of nitric oxide with the oxygen of the air

ii) Silver nitrate solution: White crystalline ppt. is obtained

iii) Turns acidified KI - starch paper blue

2KI + 2NO2 → 2KNO2 + I2

Starch + I2 → Blue colour

5. Acetate
i) Dilute Sulphuric Acid: A smell of vinegar is observed.

The following test is performed with the aqueous salt solution.

ii) Iron (III) Chloride Solution: Gives deep - red coloration

3

Brown color ppt forms

6. Thiosulphates
i) Dil Hydrochloric acid: Gives sulphur & sulphur dioxide

ii) Silver nitrate solution: Gives white ppt. of silver thiosulphate.

The ppt. is unstable, turning dark on standing when silver sulphide is formed.

iii) Lead acetate or Lead nitrate solution: Gives white ppt.

On boiling, it turns black due to the formation of PbS.
7. Chloride

Conc. : decomposes with the evolution of HCl.

-

Gas so produced

(1) Turns blue litmus paper red

(2) Gives white fumes of NH4Cl when a glass rod moistened with ammonia
solution is brought near the mouth of the test tube.

Silver nitrate solution: White, curdy ppt. of AgCl insoluble in water & in dil
.nitric acid, but soluble in dilute ammonia solution.

v) Chromyl chloride test: When a salt containing chloride ion is heated with
and conc. orange-red fumes of chromyl chloride
are formed.

A sample of chlorine-containing salt is heated with conc in presence of

, deep red vapours of chromyl chloride are evolved.

Chromyl chloride
(deep red vapour)
When these vapours are passed through a NaOH solution, the solution becomes
yellow due to the formation of sodium chromate.

The yellow solution is neutralized with acetic acid and on the addition of lead
acetate gives a yellow precipitate of lead chromate.

8. Bromide
 Conc. : Gives reddish-brown vapors of bromine accompanying
the hydrogen bromide.

Manganese dioxide and conc. sulphuric acid: When a mix of solid bromide,
, and conc. is heated reddish-brown vapors of bromine are
evolved.

The following tests are performed with the aqueous salt solution.

Silver nitrate solution: Pale yellow ppt. of silver bromide is obtained. This ppt.
is sparingly soluble in dil but readily soluble in conc. ammonia solution and
insoluble in dil.

Lead acetate solution: White crystalline ppt. of lead bromide which is

soluble in boiling water.

9. Iodide

Conc. : Gives violet vapors of iodine

Silver nitrate solution: Yellow ppt. of silver iodide AgI, very slightly soluble in
conc. ammonia solution and insoluble in dil nitric acid.

10. Nitrate

Conc : Gives reddish-brown vapors of nitrogen dioxide

Brown ring test: When freshly saturated solution of iron (II) sulfate is added
to nitrate solution and conc. H2SO4 is poured slowly down the side of the
test - tube, a brown ring is obtained.

On shaking and warming the mix, the brown color disappears, nitric oxide is
evolved and a yellow solution of Iron(III) ions remains.

11. Test for Oxalate ion [C2O24 – ]

CaCl2 + Na2C2O4 → CaC2O4 (White precipitate) + 2NaCl

12. Sulfate
i) Barium chloride solution: White ppt. of barium sulfate insoluble in
warm dil. hydrochloric acid and in dilute nitric acid but moderately soluble in
boiling, conc. hydrochloric acid.

ii) Lead acetate solution: Gives white ppt forms

Na2SO4 + (CH3COO)2Pb → PbSO4(white ppt) + 2CH3COONa

13. Test for Phosphate ion [PO3 4 –]

Na2HPO4 + 12 (NH4 )2 MoO4 + 23 HNO3 → (NH4 )3 [P (Mo3O10) 4 ] (Canary yellow

precipitate) + 2NaNO3 + 21NH4NO3 + 12H2O

Test for Cations:

Group I

gives a yellow ppt. with The ppt. is insoluble in acetic

acid but soluble in NaOH

AgCl is soluble in NH4OH forming a complex while forms a black

ppt. with .

2. Group II A

ions in solution give deep blue color with an excess of

ions give a chocolate precipitate with

For Pb2+
3PbS + 8HNO3 → 3Pb (NO3)2 + 2NO + 4H2O + 3S

Pb(NO3 )2 + H2SO4 → PbSO4 + 2HNO3

White precipitate of lead sulphate appears in the above reaction. For further
confirmation.
 PbSO4 + 4CH3COONH4 → (NH4)2 [Pb (CH3COO)4 ] + (NH4)3SO4

(NH4)2 [Pb(CH3COO)4 ] + K2CrO4 → PbCrO4 + 2CH3COOK + 2(NH4)2SO4

The Colour of PbCrO4 is yellow which confirms the presence of Pb2+.

3. Group II B

ions in solution give a yellow precipitate with ammonium molybdate

and on heating.

4. Group III A

White precipitate of is soluble in NaOH

is insoluble in NaOH

Brown precipitate of is dissolved in HCl and addition of KCNS to

this solution gives blood red color.

Also on the addition of K4Fe(CN)6 to this solution, a Prussian blue color is

obtained.

5. Group IV

after conversion into NiCl2 forms a red ppt with dimethyl glyoxime.

Co2+ ion forms a yellow ppt in the following reaction.

CoCl2 + 7KNO2 + 2CH3COOH → K3 [Co(NO2) 6] + 2KCl + 2CH3COOK + NO + H2O

ions in solution give a white precipitate with NaOH, which dissolves in

excess of NaOH.
 Mn2+ ions in solution give a pink precipitate with NaOH turning black or
brown on heating.

6. Group V

ions in solution give yellow precipitate with

ions give a white precipitate with .

ions give a white precipitate with only.

7. Group VI
For Mg2+, white ppt of Magnesium ammonium phosphate forms as shown in
below reaction.

Mg2+ + Na2HPO4 → Mg (NH4 )PO4 + NH4OH + 2Na+ + H2O

8. Group 0
NH4+ ion can be formed by the following reaction sequence.

(NH4)2SO4 + 2NaOH → Na2 SO4 + 2NH3 + 2H2O

NH3 + HCl → NH4Cl(white)

2K2HgI4 + NH3 + 3KOH → HgO.Hg(NH2)I(Brown precipitate) + 7KI + 2H2O

Importance of Inorganic Chemistry Principles of Qualitative

Analysis
The qualitative analysis of a substance helps in the determination of the physical
and chemical properties of a compound, element, or ion. There are different
types of qualitative analysis methods that are covered in this chapter.

This chapter will introduce how different extracts are formulated and then
analyzed to understand the qualitative features of compounds. These
techniques can also be used in the analysis of organic compounds.

It will describe how different methods are used for analysing and confirming the
presence of particular elements, ions, functional groups, and compounds.